CN111342032B - Preparation method and application of oriented graphene coated silica material - Google Patents

Preparation method and application of oriented graphene coated silica material Download PDF

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CN111342032B
CN111342032B CN202010292135.5A CN202010292135A CN111342032B CN 111342032 B CN111342032 B CN 111342032B CN 202010292135 A CN202010292135 A CN 202010292135A CN 111342032 B CN111342032 B CN 111342032B
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rotary kiln
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oriented graphene
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organic gas
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CN111342032A (en
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薛孟尧
杨时峰
胥鑫
曹新龙
田占元
邵乐
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Shaanxi Coal and Chemical Technology Institute Co Ltd
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/362—Composites
    • H01M4/366—Composites as layered products
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/36—Selection of substances as active materials, active masses, active liquids
    • H01M4/48—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides
    • H01M4/483—Selection of substances as active materials, active masses, active liquids of inorganic oxides or hydroxides for non-aqueous cells
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/624—Electric conductive fillers
    • H01M4/625—Carbon or graphite
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/62—Selection of inactive substances as ingredients for active masses, e.g. binders, fillers
    • H01M4/628—Inhibitors, e.g. gassing inhibitors, corrosion inhibitors
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
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    • H—ELECTRICITY
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    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M2004/026—Electrodes composed of, or comprising, active material characterised by the polarity
    • H01M2004/027—Negative electrodes
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Abstract

A preparation method and application of an oriented graphene coated silica material are disclosed, wherein the silica is put into a closed rotary kiln, and the rotary kiln is pumped to a negative pressure state; under heating, introducing organic gas into the rotary kiln, and pyrolyzing on the surface of the oxidized silica; and then introducing auxiliary gas into the rotary kiln for etching to obtain the oriented graphene coated silica material. The method disclosed by the invention is different from the traditional gas phase coating, the coated carbon material is the oriented graphene, the method has the advantages of high mechanical property, conductivity and the like of the graphene, and the vertical graphene sheets on the surfaces of different particles are mutually overlapped, so that a three-dimensional network structure can be formed, and the circulation stability of the material is facilitated. The invention can realize industrialized continuous production.

Description

Preparation method and application of oriented graphene coated silica material
Technical Field
The invention relates to the technical field of a silicon oxide material, in particular to a preparation method and application of an oriented graphene coated silicon oxide material.
Background
In recent years, along with the gradual issuance of the sale prohibition period of fuel vehicles by various countries, electric vehicles become key layout objects of various vehicle enterprises, the countries also make long-term planning on the mileage of the electric vehicles, and along with the improvement of the endurance mileage, the traditional graphite cathode is difficult to meet the requirements. The silicon negative electrode material is considered as an ideal next-generation negative electrode material, has high mass specific capacity, low lithium extraction potential and low price, but has high volume expansion (300 percent), the SEI film is continuously thickened in the circulation process, the pulverization and the falling of the material seriously limit the application of the silicon negative electrode material, and compared with the silicon negative electrode, the silicon monoxide has lower expansion (160 percent) and better cycle performance, thereby receiving wide attention of people.
In order to improve the electrochemical performance of the silicon oxide, the carbon coating is a method which is simple, convenient and feasible and is convenient for scale-up production. Commonly used carbon coating methods are gas phase coating, solid phase coating and liquid phase coating.
In CN 104022257A, a layer of pyrolytic carbon is coated on the surface of the silicon oxide by a solid phase coating method, the first effect and the cycle performance of the silicon oxide are improved to a certain extent, but the solid phase coating often has the characteristic of uneven coating, and the surface of the silicon oxide still has a bare and leaky interface, which is not beneficial to the long cycle of the battery.
Disclosure of Invention
In order to overcome the problems in the prior art, the invention aims to provide a preparation method and application of an oriented graphene coated silica material.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of an oriented graphene coated silica material comprises the following steps:
s1, putting the silicon monoxide into a sealed rotary kiln, and pumping the rotary kiln to a negative pressure state;
s2, under heating, introducing organic gas into the rotary kiln, and pyrolyzing on the surface of the silica oxide;
and S3, introducing auxiliary gas into the rotary kiln, and etching to obtain the oriented graphene coated silica material.
The invention is further improved in that in step S1, the vacuum degree in the rotary kiln is pumped to 0.1-20 KPa.
The invention is further improved in that in step S2, organic gas is introduced to maintain the pressure in the rotary kiln at 30-35 KPa.
In a further improvement of the present invention, in step S2, the organic gas is one or a mixture of two or more of methane, ethane, ethylene, propylene, acetylene, and propyne.
The invention is further improved in that in step S2, the heating temperature is 800-900 ℃.
The further improvement of the present invention is that in step S2, when the dosage of the silicon monoxide is 1.5kg, the time for introducing the organic gas is 120-150min, and the flow rate of the organic gas is 1-10L/min.
In a further improvement of the present invention, in step S3, the auxiliary gas is a mixture of hydrogen and ammonia.
The invention is further improved in that the volume ratio of hydrogen to ammonia is 1: (0.1-0.5), the volume ratio of the auxiliary gas to the organic gas is 1: (5-8).
The invention is further improved in that in the step S3, the auxiliary gas is introduced for 20-30 min.
The oriented graphene coated silica material prepared by the method is applied as a lithium ion battery negative electrode material.
Compared with the prior art, the invention has the following beneficial effects: in the circulating process of the silicon monoxide, the silicon monoxide has expansion of up to 160 percent, so that the electrode material is easy to fall off and pulverize, the expansion of the silicon monoxide can be effectively inhibited by coating a layer of carbon material on the surface, and the interface between the surface carbon layer and the graphite also influences the circulating performance of the battery. The cycle performance of the battery can be effectively improved by coating the surface with the oriented graphene. The method disclosed by the invention is different from the traditional gas phase coating, the coated carbon material is the oriented graphene, the method has the advantages of high mechanical property, conductivity and the like of the graphene, and the vertical graphene sheets on the surfaces of different particles are mutually overlapped, so that a three-dimensional network structure can be formed, and the circulation stability of the material is facilitated. The invention can realize industrialized continuous production.
Drawings
FIG. 1 is a transmission electron microscope image of example 1 of the present invention;
FIG. 2 is a graph comparing the first coulombic efficiency performance of example 1 with conventional vapor cladding;
FIG. 3 is a graph comparing the cycle performance of example 1 with conventional gas phase coating.
FIG. 4 is a transmission electron micrograph of the sample obtained in example 2.
FIG. 5 is a transmission electron micrograph of the sample obtained in example 3.
FIG. 6 is a transmission electron micrograph of the sample obtained in example 4.
Detailed Description
A battery anode material with oriented graphene coated with silicon monoxide comprises the following steps:
and S1, putting the silicon monoxide into a sealed intermittent rotary kiln, and pumping partial gas in the rotary kiln by using a vacuum pump to keep a certain negative pressure state.
And S2, raising the temperature, and introducing a certain amount of organic gas into the rotary kiln, wherein the organic gas is pyrolyzed on the surface of the silicon oxide.
And S3, introducing hydrogen and ammonia gas, and etching to obtain the oriented silicon oxide/graphene composite material.
Preferably, in S1, after the vacuum degree in the furnace chamber is pumped to 10 to 20KPa, the organic gas is introduced, so that the pressure in the furnace chamber is maintained at 30 to 35 KPa.
Preferably, the organic gas in S2 is one or a mixture of two or more of methane, ethane, ethylene, propylene, acetylene, and propyne.
Preferably, the temperature in the S2 is 800-900 ℃.
Preferably, when the amount of the silicon monoxide in the S2 is 1.5kg, the time for introducing the organic gas is 120-150min, and the flow rate of the organic gas is 1-10L/min.
Preferably, the auxiliary gas introduced in S3 is a mixed gas of hydrogen and ammonia, and the volume ratio of the auxiliary gas to the organic gas is 1: (5-8).
Preferably, the introducing time of the mixed gas of hydrogen and ammonia in the S3 is 20-30 min.
The oriented graphene coated silicon oxide material prepared by the invention is applied as a lithium ion battery cathode material.
The following are specific examples.
Example 1
1.5kg of silica was placed in a closed batch rotary kiln, and a predetermined amount of nitrogen was introduced to replace the air in the kiln. The rotary kiln was then evacuated to 0.1KPa, the vacuum was then maintained and the temperature was increased to 900 ℃. Introducing a certain amount of methane to the pressure of about 30Kpa, and keeping the temperature for 120min to form a graphene layer on the surface of the silicon oxide. Then introducing hydrogen in a volume ratio of: ammonia gas 2: 1, etching the graphene layer on the surface of the silicon oxide for 20min, wherein the volume ratio of the mixed gas of hydrogen and ammonia to methane is 1: and 5, obtaining the oriented graphene coated silicon oxide negative electrode material.
A TEM for detecting the morphology of the oriented graphene coated silica material obtained in example 1 is shown in fig. 1.
As can be seen from fig. 1, the graphene-coated silica material prepared in example 1 has a layer of vertically oriented graphene on the surface of the silica.
The button cell is prepared by using the oriented graphene-coated silicon oxide material prepared in example 1 as a negative electrode material, and the button cell is prepared by using the carbon-coated silicon oxide material prepared by a conventional vapor phase method as a negative electrode material, and the first charge-discharge test and the cycle performance test are performed on the two materials, and the test results are shown in fig. 2 and 3.
As shown in fig. 2, the button cell made of the oriented graphene-coated silicon oxide material prepared in example 1 has higher first coulombic efficiency than the conventional vapor phase coating method.
As shown in fig. 3, compared with the conventional vapor phase carbon coating method, the button cell made of the oriented graphene coated silicon oxide material prepared in example 1 has significantly improved cycle performance of the silicon oxide material.
Example 2
1.5kg of silica is put into a rotary kiln, a certain amount of nitrogen is introduced, the air in the kiln is replaced, and the vacuum is pumped to 0.1 Kpa. The temperature is increased to 900 ℃. Introducing a certain amount of methane instead of nitrogen, keeping the pressure at about 30Kpa, and keeping the temperature for 120min to form a graphene layer on the surface of the silicon oxide. Then introducing hydrogen with a volume ratio to etch the graphene layer on the surface of the silicon oxide for 20min, wherein the volume ratio of the hydrogen to the methane is 1: and 5, obtaining the graphene-coated silicon oxide negative electrode material with weaker orientation.
A TEM for examining the morphology of the oriented graphene coated silica material obtained in example 2 is shown in fig. 4.
As can be seen from fig. 4, the graphene-coated silica material prepared in example 2 has a layer of graphene with weak vertical orientation on the surface of the silica.
As can be seen from a comparison of fig. 1 and 4, the etching effect of hydrogen gas and ammonia gas is a key to the formation of oriented graphene.
Example 3
1.5kg of silica is put into a rotary kiln, a certain amount of nitrogen is introduced, the air in the kiln is replaced, and the vacuum is pumped to 0.1 Kpa. The temperature is increased to 900 ℃. And introducing a certain amount of methane to replace nitrogen, and keeping the temperature for 120min to obtain the graphene-coated silicon oxide composite material.
A TEM for examining the morphology of the oriented graphene coated silica material obtained in example 3 is shown in fig. 5.
As can be seen from fig. 5, the surface of the oriented graphene-coated silica material prepared in example 3 is not oriented graphene.
Example 4
Only the pyrolysis of the carbon source (i.e., organic gas) was changed to acetylene as in example 1.
A TEM for examining the morphology of the oriented graphene coated silica material obtained in example 4 is shown in fig. 6.
As can be seen from fig. 6, the oriented graphene oxide material prepared in example 6 has a surface with oriented graphene but has a weak orientation.
Example 5
1.5kg of silica was placed in a closed batch rotary kiln, and a predetermined amount of nitrogen was introduced to replace the air in the kiln. The rotary kiln was then evacuated to 20KPa, the vacuum was then maintained and the temperature was raised to 800 ℃. And introducing a certain amount of organic gas until the pressure is about 30Kpa, and keeping the temperature for 120min, wherein the flow of the organic gas is 1L/min, so that the graphene layer is formed on the surface of the silicon oxide. Then introducing hydrogen in a volume ratio of: ammonia gas 1: and (3) etching the graphene layer on the surface of the silicon oxide for 20min by using the mixed gas of 0.5, wherein the volume ratio of the mixed gas of hydrogen and ammonia to the organic gas is 1: and 5, obtaining the oriented graphene coated silicon oxide negative electrode material. Wherein the organic gas is ethane.
Example 6
1.5kg of silica was placed in a closed batch rotary kiln, and a predetermined amount of nitrogen was introduced to replace the air in the kiln. The rotary kiln was then evacuated to 10KPa, the vacuum was then maintained and the temperature was raised to 820 ℃. And introducing a certain amount of organic gas until the pressure is about 32Kpa, and keeping the temperature for 150min, wherein the flow of the organic gas is 10L/min, so that the graphene layer is formed on the surface of the silicon oxide. Then introducing hydrogen in a volume ratio of: ammonia gas 1: and (3) etching the graphene layer on the surface of the silicon oxide for 30min by using the mixed gas of 0.1, wherein the volume ratio of the mixed gas of hydrogen and ammonia to the organic gas is 1: and 6, obtaining the oriented graphene coated silicon oxide negative electrode material. Wherein the organic gas is ethylene.
Example 7
1.5kg of silica was placed in a closed batch rotary kiln, and a predetermined amount of nitrogen was introduced to replace the air in the kiln. The rotary kiln was then evacuated to 1KPa, the vacuum was then maintained and the temperature was raised to 850 ℃. And introducing a certain amount of organic gas until the pressure is about 33Kpa, and keeping the temperature for 140min, wherein the flow of the organic gas is 5L/min, so that the graphene layer is formed on the surface of the silicon oxide. Then introducing hydrogen in a volume ratio of: ammonia gas 1: and (3) etching the graphene layer on the surface of the silicon oxide for 25min by using the mixed gas of 0.2, wherein the volume ratio of the mixed gas of hydrogen and ammonia to the organic gas is 1: and 7, obtaining the oriented graphene coated silicon oxide negative electrode material. Wherein the organic gas is a mixed gas of propylene and acetylene.
Example 8
1.5kg of silica was placed in a closed batch rotary kiln, and a predetermined amount of nitrogen was introduced to replace the air in the kiln. The rotary kiln was then evacuated to 5KPa, the vacuum was then maintained and the temperature was raised to 880 ℃. And introducing a certain amount of organic gas until the pressure is about 35Kpa, and keeping the temperature for 130min, wherein the flow of the organic gas is 8L/min, so that the graphene layer is formed on the surface of the silicon oxide. Then introducing hydrogen in a volume ratio of: ammonia gas 1: and (3) etching the graphene layer on the surface of the silicon oxide for 20min by using the mixed gas of 0.3, wherein the volume ratio of the mixed gas of hydrogen and ammonia to the organic gas is 1: and 8, obtaining the oriented graphene coated silicon oxide negative electrode material. Wherein the organic gas is a mixed gas of propane, methane and ethane.
Example 9
1.5kg of silica was placed in a closed batch rotary kiln, and a predetermined amount of nitrogen was introduced to replace the air in the kiln. The rotary kiln was then evacuated to 15KPa, the vacuum was then maintained and the temperature was raised to 900 ℃. And introducing a certain amount of organic gas until the pressure is about 30Kpa, and keeping the temperature for 120min, wherein the flow of the organic gas is 3L/min, so that the graphene layer is formed on the surface of the silicon oxide. Then introducing hydrogen in a volume ratio of: ammonia gas 1: and (3) etching the graphene layer on the surface of the silicon oxide for 30min by using the mixed gas of 0.4, wherein the volume ratio of the mixed gas of hydrogen and ammonia to the organic gas is 1: and 5, obtaining the oriented graphene coated silicon oxide negative electrode material. Wherein the organic gas is a mixed gas of ethylene and propylene.
Compared with the mainstream product prepared by the traditional method, the oriented graphene coated silica material prepared by the method has better performance.

Claims (8)

1. A preparation method of an oriented graphene coated silica material is characterized by comprising the following steps:
s1, putting the silicon monoxide into a sealed rotary kiln, and pumping the rotary kiln to a negative pressure state;
s2, under heating, introducing organic gas into the rotary kiln, and pyrolyzing on the surface of the silica oxide;
s3, introducing auxiliary gas into the rotary kiln, and etching to obtain the oriented graphene coated silica material; wherein the auxiliary gas is a mixed gas of hydrogen and ammonia.
2. The method for preparing the oriented graphene coated silica material according to claim 1, wherein in step S1, the vacuum degree in the rotary kiln is pumped to 0.1-20 KPa.
3. The method for preparing the oriented graphene coated silica material according to claim 1, wherein in step S2, an organic gas is introduced to maintain the pressure in the rotary kiln at 30-35 KPa.
4. The method of claim 1, wherein in step S2, the organic gas is one or a mixture of two or more of methane, ethane, ethylene, propylene, acetylene, and propyne.
5. The method as claimed in claim 1, wherein the heating temperature in step S2 is 800-900 ℃.
6. The method as claimed in claim 1, wherein in step S2, when the amount of the silicon oxide is 1.5kg, the time for introducing the organic gas is 120-150min, and the flow rate of the organic gas is 1-10L/min.
7. The method for preparing an oriented graphene coated silica material according to claim 1, wherein the volume ratio of hydrogen to ammonia is 1: (0.1-0.5), the volume ratio of the auxiliary gas to the organic gas is 1: (5-8).
8. The method of claim 1, wherein in step S3, the time for introducing the auxiliary gas is 20-30 min.
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